A two-dimensional manganese(II) complex: poly[bis­(μ2-4,4′-bipyrid­yl)tetra­kis­(μ2-3,5-dinitro­benzoato)dimanganese(II)]

Wang, J.; Li, Z.-L.; Xu, X.-Z.; Yan, W.-J.

doi:10.1107/S1600536810034495

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 10| October 2010| Page m1187

doi:10.1107/S1600536810034495

Open

access

A two-dimensional manganese(II) complex: poly[bis(μ₂-4,4′-bipyridyl)tetrakis(μ₂-3,5-dinitrobenzoato)dimanganese(II)]

Jian Wang,^a Zhu-Lai Li,^a ^* Xiu-Zhi Xu ^a and Wen-Jin Yan ^a

^aDepartment of Medicinal Chemistry, School of Pharmacy, Fujian Medical University, Fuzhou, Fujian 350004, People's Republic of China
^*Correspondence e-mail: lizhulai@126.com

(Received 16 August 2010; accepted 26 August 2010; online 4 September 2010)

The Mn atom in the title compound, [Mn₂(C₇H₃N₂O₆)₄(C₁₀H₈N₂)₂]_n, is six-coordinated by two N atoms and four O atoms, forming a distorted octahedral geometry. The Mn—O bond lengths are in the range 2.1281 (13)–2.2011 (12) Å and the Mn—N bond lengths are 2.269 (2) and 2.278 (2) Å. Mn(II) atoms are double-bridged along the a axis by two pairs of bi-monodentate carboxyl groups, forming a double-stranded chain, while the bidentate 4,4′-bipyridine ligand bridges the Mn atom along the b axis. This results in a two-dimensional structure constructed of oblong grids with the sides of length 11.634 and 5.075 Å

Related literature

In order to study the relationship between the manganese ion and the biological coordination agent, the role of the manganese ion in the active sites and the structure of the active sites in the manganese enzymes, small molecule complexes are often applied to modeling the structure and the properties of reaction in the active centers, see: Shi et al. (2000 ). The characterization of metal complexes containing monocarboxylic acids has demonstrated the versatility of the carboxylate group as an innersphere ligand, see: Mehrotra & Bohra (1983 ).

Experimental

Crystal data

[Mn₂(C₇H₃N₂O₆)₄(C₁₀H₈N₂)₂]
M_r = 633.35
Monoclinic, P 2/n
a = 10.0873 (6) Å
b = 11.6336 (6) Å
c = 21.2191 (12) Å
β = 98.075 (3)°
V = 2465.41 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.62 mm⁻¹
T = 293 K
0.82 × 0.45 × 0.35 mm

Data collection

Rigaku Mercury diffractometer
Absorption correction: multi-scan (CrystalStructure; Rigaku, 2000 ) T_min = 0.779, T_max = 1.000
14626 measured reflections
4334 independent reflections
4149 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.085
S = 1.01
4334 reflections
393 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Data collection: CrystalClear Rigaku (2000); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810034495/br2146sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810034495/br2146Isup2.hkl

checkCIF report

Comment top

In order to study the relationship between the manganese ion and the biological coordination agent, the role of manganese ion in the active sites and the structure of the active sites in the manganese enzymes, small molecule complexes are often applied to modeling the structure and the properties of reaction in the active centers (Shi et al.2000). Metal complexes containing monocarboxylic acids are well known and the publication of many structurally characterized examples of this class of compounds has demonstrated the versatility of the carboxylate group as an innersphere ligand (Mehrotra et al., 1983). In this paper, we will report the synthesis and crystal structure of a new two-dimensional manganese complex, [Mn₂.(dinitrobenzoic acid)₄.(4,4-bipy)₂]n,(I). The crystal structure was confirmeded by X-ray crystallography.

The crystal structure of the title compound is illustrated in Fig.1. The Mn atom is located in an octahedral enviroment containing two N from two bipy ligand, four O from two chelating carboxyl. The Mn—O bond lengths are in the range 2.1281 (13) - 2.2011 (12) Å, and the Mn—N bond lengths are 2.269 (2) and 2.278 (2) Å.

Along the a axis, each Mn(II) center is double-bridged by two pair of bi-monodentate carboxyl, and forming a double-stranded chain. Along the b axis, the bidentate ligand 4,4'-bipyridine bridge the Mn atom in a straight mode. As a result, the whole molecule features a two-dimensional structure constructed of oblong grids with the side length 11.634 and 5.075 Å, as shown in Fig.2.

Related literature top

Experimental top

The reaction of dinitrobenzoic acid 0.636 g(3 mmol) and NaOH 0.12 g(3 mmol) in the molar ratio of 1:1 in an aqueous-alcohol(3:1) solution(40 ml) at room temperature for 30 minutes produced a colorless solution, to which MnCl₂.6H₂O 0.198 g(1 mmol) and 4,4'-bipyridine 0.156 g(1 mmol) was added to produced a yellowy solution. The reaction solution was kept at room temperature after stirring for an hour. Yellowy crystals were obtained after a few days, which were washed with water and ethanol for several times and then dried in air.

Computing details top

Data collection: CrystalClear (Rigaku, 2000); cell refinement: CrystalClear (Rigaku, 2000); data reduction: CrystalClear (Rigaku, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the structure of the title compound, showing 30% probability displacement ellipsoids. H atoms have been omitted for clarity. Symmetry codes: (A) -x+1/2, y, -z+1/2; (B) -x+3/2, y, -z+1/2; (C) x, y+1, z;(D) x, y-1, z.
	Fig. 2. The two-dimensional structure of the title compound, constructed of oblong grids. Only the carboxyl group of the benzoic acid is shown for clarity.

poly[bis(µ₂-4,4'-bipyridyl)tetrakis(µ₂-3,5- dinitrobenzoato)dimanganese(II)] top

Crystal data top

[Mn₂(C₇H₃N₂O₆)₄(C₁₀H₈N₂)₂]	F(000) = 1284
M_r = 633.35	D_x = 1.706 Mg m⁻³
Monoclinic, P2/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yac	Cell parameters from 5503 reflections
a = 10.0873 (6) Å	θ = 1.9–25.0°
b = 11.6336 (6) Å	µ = 0.62 mm⁻¹
c = 21.2191 (12) Å	T = 293 K
β = 98.075 (3)°	Prism, yellow
V = 2465.41 (14) Å³	0.82 × 0.45 × 0.35 mm
Z = 4

Data collection top

Rigaku Mercury diffractometer	4334 independent reflections
Radiation source: fine-focus sealed tube	4149 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
ω scans	θ_max = 25.0°, θ_min = 2.0°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2000)	h = −12→9
T_min = 0.779, T_max = 1.000	k = −13→13
14626 measured reflections	l = −23→25

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.085	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0435P)² + 1.780P] where P = (F_o² + 2F_c²)/3
4334 reflections	(Δ/σ)_max < 0.001
393 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.37 e Å⁻³

Crystal data top

[Mn₂(C₇H₃N₂O₆)₄(C₁₀H₈N₂)₂]	V = 2465.41 (14) Å³
M_r = 633.35	Z = 4
Monoclinic, P2/n	Mo Kα radiation
a = 10.0873 (6) Å	µ = 0.62 mm⁻¹
b = 11.6336 (6) Å	T = 293 K
c = 21.2191 (12) Å	0.82 × 0.45 × 0.35 mm
β = 98.075 (3)°

Data collection top

Rigaku Mercury diffractometer	4334 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2000)	4149 reflections with I > 2σ(I)
T_min = 0.779, T_max = 1.000	R_int = 0.018
14626 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.085	H-atom parameters constrained
S = 1.01	Δρ_max = 0.31 e Å⁻³
4334 reflections	Δρ_min = −0.37 e Å⁻³
393 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Mn1	0.2500	0.19545 (3)	0.2500	0.01900 (11)
Mn2	0.7500	0.24424 (3)	0.2500	0.02079 (11)
O1	0.39680 (12)	0.20294 (11)	0.33670 (6)	0.0285 (3)
O2	0.59377 (14)	0.24937 (13)	0.30771 (7)	0.0376 (3)
O3	0.60065 (13)	0.24451 (12)	0.16375 (6)	0.0317 (3)
C13	0.51107 (17)	0.24788 (14)	0.34545 (8)	0.0228 (4)
N4	0.7500	1.04904 (18)	0.2500	0.0289 (5)
O4	0.39999 (13)	0.19047 (13)	0.18644 (6)	0.0378 (3)
C3	0.2500	−0.2403 (2)	0.2500	0.0233 (5)
C9	0.7500	0.6807 (2)	0.2500	0.0266 (5)
N3	0.7500	0.43988 (18)	0.2500	0.0292 (5)
C10	0.7500	0.8084 (2)	0.2500	0.0265 (5)
N1	0.2500	0.00037 (17)	0.2500	0.0256 (4)
O11	0.1529 (2)	−0.04745 (19)	−0.06614 (9)	0.0772 (7)
C15	0.48226 (19)	0.28563 (16)	0.45950 (9)	0.0295 (4)
H15	0.4092	0.2361	0.4548	0.035*
N8	0.1882 (2)	−0.02270 (18)	−0.01070 (9)	0.0527 (5)
C26	0.33672 (19)	0.09265 (16)	0.06677 (9)	0.0302 (4)
H26	0.2875	0.0686	0.0983	0.036*
C2	0.30203 (19)	−0.17792 (15)	0.30368 (9)	0.0294 (4)
H2	0.3357	−0.2158	0.3411	0.035*
C21	0.44557 (17)	0.16499 (15)	0.08170 (8)	0.0237 (4)
N2	0.2500	−0.60873 (17)	0.2500	0.0247 (4)
C14	0.55181 (18)	0.30668 (15)	0.40903 (8)	0.0255 (4)
C4	0.2500	−0.3681 (2)	0.2500	0.0235 (5)
N5	0.4524 (2)	0.31431 (18)	0.57173 (8)	0.0447 (5)
C1	0.30335 (19)	−0.05938 (15)	0.30107 (9)	0.0290 (4)
H1	0.3433	−0.0192	0.3366	0.035*
O5	0.3718 (3)	0.2385 (3)	0.56666 (10)	0.1090 (11)
C20	0.48563 (17)	0.20357 (14)	0.15039 (8)	0.0228 (4)
C19	0.66089 (18)	0.38110 (16)	0.41675 (9)	0.0315 (4)
H19	0.7101	0.3942	0.3835	0.038*
C11	0.6523 (2)	0.87052 (17)	0.27427 (11)	0.0407 (5)
H11	0.5844	0.8325	0.2913	0.049*
C6	0.22428 (19)	−0.54874 (15)	0.30084 (8)	0.0276 (4)
H6	0.2067	−0.5890	0.3366	0.033*
C8	0.8668 (2)	0.61846 (17)	0.26293 (12)	0.0434 (5)
H8	0.9485	0.6563	0.2718	0.052*
C16	0.52304 (19)	0.33937 (17)	0.51722 (9)	0.0318 (4)
O12	0.1347 (2)	−0.0599 (2)	0.03319 (10)	0.0937 (9)
C5	0.22266 (18)	−0.42997 (15)	0.30270 (8)	0.0269 (4)
H5	0.2035	−0.3918	0.3389	0.032*
C17	0.6271 (2)	0.41653 (17)	0.52608 (9)	0.0345 (4)
H17	0.6507	0.4542	0.5647	0.041*
O10	0.5122 (2)	0.1732 (2)	−0.13269 (8)	0.0763 (7)
O6	0.48179 (19)	0.36920 (17)	0.62041 (7)	0.0610 (5)
N7	0.54582 (19)	0.20781 (19)	−0.07935 (8)	0.0457 (5)
C7	0.8626 (2)	0.49998 (17)	0.26272 (12)	0.0436 (5)
H7	0.9428	0.4600	0.2720	0.052*
C22	0.51562 (18)	0.20179 (16)	0.03395 (9)	0.0288 (4)
H22	0.5893	0.2500	0.0432	0.035*
C23	0.47448 (19)	0.16581 (17)	−0.02799 (8)	0.0307 (4)
C24	0.36823 (19)	0.09225 (17)	−0.04444 (9)	0.0326 (4)
H24	0.3428	0.0682	−0.0862	0.039*
O9	0.6350 (2)	0.2753 (3)	−0.06612 (9)	0.0986 (9)
C12	0.6554 (2)	0.98865 (17)	0.27332 (11)	0.0409 (5)
H12	0.5881	1.0285	0.2898	0.049*
N6	0.8062 (2)	0.51773 (19)	0.48328 (11)	0.0562 (6)
C25	0.30197 (19)	0.05647 (17)	0.00456 (9)	0.0326 (4)
C18	0.69470 (19)	0.43534 (17)	0.47508 (10)	0.0356 (5)
O7	0.8276 (2)	0.5696 (2)	0.53379 (11)	0.0904 (8)
O8	0.8707 (2)	0.5303 (2)	0.43984 (12)	0.0902 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0216 (2)	0.01424 (19)	0.02138 (19)	0.000	0.00381 (14)	0.000
Mn2	0.0215 (2)	0.01626 (19)	0.0247 (2)	0.000	0.00365 (14)	0.000
O1	0.0259 (7)	0.0332 (7)	0.0253 (6)	−0.0066 (5)	0.0001 (5)	0.0004 (5)
O2	0.0320 (7)	0.0491 (9)	0.0339 (7)	−0.0046 (6)	0.0124 (6)	−0.0083 (6)
O3	0.0273 (7)	0.0408 (8)	0.0261 (7)	−0.0089 (6)	0.0006 (5)	0.0002 (6)
C13	0.0231 (9)	0.0201 (8)	0.0246 (9)	0.0025 (7)	0.0009 (7)	0.0027 (7)
N4	0.0333 (12)	0.0192 (10)	0.0350 (12)	0.000	0.0079 (9)	0.000
O4	0.0292 (7)	0.0581 (9)	0.0283 (7)	−0.0048 (6)	0.0117 (6)	−0.0079 (6)
C3	0.0243 (13)	0.0157 (12)	0.0301 (13)	0.000	0.0041 (10)	0.000
C9	0.0300 (13)	0.0201 (12)	0.0301 (13)	0.000	0.0059 (11)	0.000
N3	0.0265 (11)	0.0195 (10)	0.0409 (13)	0.000	0.0028 (9)	0.000
C10	0.0298 (13)	0.0194 (12)	0.0294 (13)	0.000	0.0009 (11)	0.000
N1	0.0272 (11)	0.0172 (10)	0.0329 (11)	0.000	0.0061 (9)	0.000
O11	0.0918 (15)	0.0888 (15)	0.0484 (11)	−0.0533 (12)	0.0010 (10)	−0.0245 (10)
C15	0.0276 (9)	0.0302 (9)	0.0296 (10)	0.0000 (8)	0.0004 (8)	−0.0021 (8)
N8	0.0582 (13)	0.0540 (12)	0.0446 (11)	−0.0287 (10)	0.0026 (9)	−0.0110 (9)
C26	0.0309 (10)	0.0306 (10)	0.0297 (10)	−0.0051 (8)	0.0065 (8)	−0.0023 (8)
C2	0.0355 (10)	0.0211 (9)	0.0300 (10)	0.0026 (8)	−0.0003 (8)	0.0011 (7)
C21	0.0229 (8)	0.0238 (8)	0.0244 (9)	0.0023 (7)	0.0031 (7)	−0.0018 (7)
N2	0.0307 (11)	0.0168 (10)	0.0261 (11)	0.000	0.0021 (9)	0.000
C14	0.0241 (9)	0.0228 (9)	0.0283 (9)	0.0039 (7)	−0.0006 (7)	−0.0017 (7)
C4	0.0230 (12)	0.0170 (12)	0.0294 (13)	0.000	−0.0001 (10)	0.000
N5	0.0488 (11)	0.0559 (12)	0.0288 (9)	0.0035 (10)	0.0029 (8)	−0.0019 (8)
C1	0.0344 (10)	0.0207 (9)	0.0314 (10)	0.0010 (8)	0.0032 (8)	−0.0046 (7)
O5	0.129 (2)	0.155 (2)	0.0501 (12)	−0.092 (2)	0.0402 (13)	−0.0271 (14)
C20	0.0235 (9)	0.0208 (8)	0.0242 (9)	0.0028 (7)	0.0037 (7)	−0.0009 (7)
C19	0.0258 (9)	0.0296 (10)	0.0387 (10)	0.0010 (8)	0.0029 (8)	−0.0025 (8)
C11	0.0405 (11)	0.0227 (10)	0.0640 (14)	−0.0020 (9)	0.0255 (10)	0.0008 (9)
C6	0.0373 (10)	0.0213 (9)	0.0244 (9)	−0.0011 (7)	0.0053 (7)	0.0016 (7)
C8	0.0258 (10)	0.0238 (10)	0.0782 (16)	−0.0040 (8)	−0.0008 (10)	−0.0016 (10)
C16	0.0331 (10)	0.0334 (10)	0.0279 (10)	0.0075 (8)	0.0006 (8)	−0.0004 (8)
O12	0.1066 (17)	0.1188 (19)	0.0565 (12)	−0.0850 (16)	0.0147 (11)	−0.0096 (12)
C5	0.0331 (10)	0.0217 (9)	0.0259 (9)	0.0005 (7)	0.0041 (7)	−0.0034 (7)
C17	0.0354 (11)	0.0319 (10)	0.0329 (10)	0.0088 (8)	−0.0072 (8)	−0.0091 (8)
O10	0.0802 (13)	0.1256 (19)	0.0245 (9)	−0.0335 (13)	0.0120 (8)	−0.0062 (10)
O6	0.0786 (12)	0.0728 (12)	0.0314 (8)	0.0081 (10)	0.0075 (8)	−0.0120 (8)
N7	0.0422 (11)	0.0696 (13)	0.0261 (9)	−0.0103 (10)	0.0076 (8)	0.0012 (9)
C7	0.0258 (10)	0.0231 (10)	0.0790 (16)	0.0016 (8)	−0.0033 (10)	−0.0001 (10)
C22	0.0249 (9)	0.0332 (10)	0.0280 (9)	−0.0032 (7)	0.0029 (7)	−0.0015 (7)
C23	0.0305 (10)	0.0385 (10)	0.0236 (9)	0.0000 (8)	0.0056 (7)	0.0013 (8)
C24	0.0359 (10)	0.0350 (10)	0.0254 (9)	0.0022 (8)	−0.0005 (8)	−0.0059 (8)
O9	0.0972 (17)	0.160 (2)	0.0429 (11)	−0.0870 (17)	0.0259 (11)	−0.0133 (12)
C12	0.0427 (12)	0.0220 (10)	0.0631 (14)	0.0029 (9)	0.0251 (10)	−0.0008 (9)
N6	0.0444 (11)	0.0505 (12)	0.0721 (15)	−0.0161 (10)	0.0029 (11)	−0.0210 (11)
C25	0.0321 (10)	0.0300 (10)	0.0347 (10)	−0.0075 (8)	0.0018 (8)	−0.0055 (8)
C18	0.0273 (10)	0.0277 (10)	0.0487 (12)	−0.0003 (8)	−0.0053 (9)	−0.0079 (9)
O7	0.0861 (15)	0.0873 (16)	0.0976 (17)	−0.0454 (13)	0.0123 (13)	−0.0546 (14)
O8	0.0725 (14)	0.1070 (18)	0.0951 (16)	−0.0562 (13)	0.0260 (12)	−0.0321 (14)

Geometric parameters (Å, º) top

Mn1—O4ⁱ	2.1644 (13)	C26—H26	0.9300
Mn1—O4	2.1644 (13)	C2—C1	1.380 (3)
Mn1—O1	2.1954 (12)	C2—H2	0.9300
Mn1—O1ⁱ	2.1954 (12)	C21—C22	1.382 (3)
Mn1—N1	2.269 (2)	C21—C20	1.524 (2)
Mn1—N2ⁱⁱ	2.278 (2)	N2—C6	1.340 (2)
Mn2—O2ⁱⁱⁱ	2.1281 (13)	N2—C6ⁱ	1.340 (2)
Mn2—O2	2.1281 (13)	N2—Mn1^iv	2.278 (2)
Mn2—O3	2.2011 (12)	C14—C19	1.391 (3)
Mn2—O3ⁱⁱⁱ	2.2011 (12)	C4—C5ⁱ	1.390 (2)
Mn2—N4^iv	2.271 (2)	C4—C5	1.390 (2)
Mn2—N3	2.276 (2)	N5—O5	1.194 (3)
O1—C13	1.255 (2)	N5—O6	1.215 (2)
O2—C13	1.235 (2)	N5—C16	1.470 (3)
O3—C20	1.249 (2)	C1—H1	0.9300
C13—C14	1.517 (2)	C19—C18	1.388 (3)
N4—C12	1.335 (2)	C19—H19	0.9300
N4—C12ⁱⁱⁱ	1.335 (2)	C11—C12	1.375 (3)
N4—Mn2ⁱⁱ	2.271 (2)	C11—H11	0.9300
O4—C20	1.241 (2)	C6—C5	1.382 (3)
C3—C2	1.390 (2)	C6—H6	0.9300
C3—C2ⁱ	1.390 (2)	C8—C7	1.379 (3)
C3—C4	1.487 (3)	C8—H8	0.9300
C9—C8ⁱⁱⁱ	1.377 (2)	C16—C17	1.374 (3)
C9—C8	1.377 (2)	C5—H5	0.9300
C9—C10	1.485 (3)	C17—C18	1.375 (3)
N3—C7	1.329 (2)	C17—H17	0.9300
N3—C7ⁱⁱⁱ	1.329 (2)	O10—N7	1.205 (2)
C10—C11ⁱⁱⁱ	1.379 (2)	N7—O9	1.198 (3)
C10—C11	1.379 (2)	N7—C23	1.471 (2)
N1—C1ⁱ	1.335 (2)	C7—H7	0.9300
N1—C1	1.335 (2)	C22—C23	1.386 (3)
O11—N8	1.215 (3)	C22—H22	0.9300
C15—C14	1.382 (3)	C23—C24	1.378 (3)
C15—C16	1.385 (3)	C24—C25	1.377 (3)
C15—H15	0.9300	C24—H24	0.9300
N8—O12	1.219 (3)	C12—H12	0.9300
N8—C25	1.472 (3)	N6—O8	1.209 (3)
C26—C25	1.383 (3)	N6—O7	1.223 (3)
C26—C21	1.384 (3)	N6—C18	1.470 (3)

O4ⁱ—Mn1—O4	176.93 (8)	C22—C21—C20	121.03 (16)
O4ⁱ—Mn1—O1	85.82 (5)	C26—C21—C20	119.53 (16)
O4—Mn1—O1	94.30 (5)	C6—N2—C6ⁱ	117.2 (2)
O4ⁱ—Mn1—O1ⁱ	94.30 (5)	C6—N2—Mn1^iv	121.38 (10)
O4—Mn1—O1ⁱ	85.82 (5)	C6ⁱ—N2—Mn1^iv	121.38 (10)
O1—Mn1—O1ⁱ	175.45 (7)	C15—C14—C19	119.86 (17)
O4ⁱ—Mn1—N1	88.47 (4)	C15—C14—C13	120.37 (16)
O4—Mn1—N1	88.47 (4)	C19—C14—C13	119.76 (16)
O1—Mn1—N1	92.27 (3)	C5ⁱ—C4—C5	117.6 (2)
O1ⁱ—Mn1—N1	92.27 (3)	C5ⁱ—C4—C3	121.18 (11)
O4ⁱ—Mn1—N2ⁱⁱ	91.53 (4)	C5—C4—C3	121.18 (11)
O4—Mn1—N2ⁱⁱ	91.53 (4)	O5—N5—O6	123.1 (2)
O1—Mn1—N2ⁱⁱ	87.73 (3)	O5—N5—C16	118.33 (18)
O1ⁱ—Mn1—N2ⁱⁱ	87.73 (3)	O6—N5—C16	118.5 (2)
N1—Mn1—N2ⁱⁱ	180.0	N1—C1—C2	123.20 (17)
O2ⁱⁱⁱ—Mn2—O2	176.79 (8)	N1—C1—H1	118.4
O2ⁱⁱⁱ—Mn2—O3	89.84 (5)	C2—C1—H1	118.4
O2—Mn2—O3	90.16 (5)	O4—C20—O3	127.70 (17)
O2ⁱⁱⁱ—Mn2—O3ⁱⁱⁱ	90.16 (5)	O4—C20—C21	116.05 (15)
O2—Mn2—O3ⁱⁱⁱ	89.84 (5)	O3—C20—C21	116.25 (15)
O3—Mn2—O3ⁱⁱⁱ	179.83 (7)	C18—C19—C14	118.62 (18)
O2ⁱⁱⁱ—Mn2—N4^iv	91.61 (4)	C18—C19—H19	120.7
O2—Mn2—N4^iv	91.61 (4)	C14—C19—H19	120.7
O3—Mn2—N4^iv	90.08 (4)	C12—C11—C10	120.00 (19)
O3ⁱⁱⁱ—Mn2—N4^iv	90.08 (4)	C12—C11—H11	120.0
O2ⁱⁱⁱ—Mn2—N3	88.39 (4)	C10—C11—H11	120.0
O2—Mn2—N3	88.39 (4)	N2—C6—C5	123.22 (17)
O3—Mn2—N3	89.92 (4)	N2—C6—H6	118.4
O3ⁱⁱⁱ—Mn2—N3	89.92 (4)	C5—C6—H6	118.4
N4^iv—Mn2—N3	180.0	C9—C8—C7	120.00 (19)
C13—O1—Mn1	129.61 (11)	C9—C8—H8	120.0
C13—O2—Mn2	174.27 (14)	C7—C8—H8	120.0
C20—O3—Mn2	133.90 (12)	C17—C16—C15	122.84 (18)
O2—C13—O1	126.85 (16)	C17—C16—N5	117.85 (17)
O2—C13—C14	116.55 (16)	C15—C16—N5	119.31 (18)
O1—C13—C14	116.60 (15)	C6—C5—C4	119.34 (17)
C12—N4—C12ⁱⁱⁱ	116.5 (2)	C6—C5—H5	120.3
C12—N4—Mn2ⁱⁱ	121.75 (11)	C4—C5—H5	120.3
C12ⁱⁱⁱ—N4—Mn2ⁱⁱ	121.75 (11)	C16—C17—C18	116.74 (17)
C20—O4—Mn1	171.41 (14)	C16—C17—H17	121.6
C2—C3—C2ⁱ	117.1 (2)	C18—C17—H17	121.6
C2—C3—C4	121.47 (11)	O9—N7—O10	122.9 (2)
C2ⁱ—C3—C4	121.47 (11)	O9—N7—C23	118.28 (18)
C8ⁱⁱⁱ—C9—C8	116.5 (2)	O10—N7—C23	118.85 (19)
C8ⁱⁱⁱ—C9—C10	121.73 (12)	N3—C7—C8	123.49 (19)
C8—C9—C10	121.73 (12)	N3—C7—H7	118.3
C7—N3—C7ⁱⁱⁱ	116.5 (2)	C8—C7—H7	118.3
C7—N3—Mn2	121.75 (12)	C21—C22—C23	119.06 (17)
C7ⁱⁱⁱ—N3—Mn2	121.75 (12)	C21—C22—H22	120.5
C11ⁱⁱⁱ—C10—C11	116.8 (2)	C23—C22—H22	120.5
C11ⁱⁱⁱ—C10—C9	121.62 (12)	C24—C23—C22	123.12 (17)
C11—C10—C9	121.62 (12)	C24—C23—N7	117.57 (17)
C1ⁱ—N1—C1	117.3 (2)	C22—C23—N7	119.31 (17)
C1ⁱ—N1—Mn1	121.37 (11)	C25—C24—C23	116.06 (17)
C1—N1—Mn1	121.37 (11)	C25—C24—H24	122.0
C14—C15—C16	119.02 (18)	C23—C24—H24	122.0
C14—C15—H15	120.5	N4—C12—C11	123.38 (19)
C16—C15—H15	120.5	N4—C12—H12	118.3
O11—N8—O12	123.7 (2)	C11—C12—H12	118.3
O11—N8—C25	118.4 (2)	O8—N6—O7	124.1 (2)
O12—N8—C25	117.96 (19)	O8—N6—C18	118.3 (2)
C25—C26—C21	119.33 (17)	O7—N6—C18	117.6 (2)
C25—C26—H26	120.3	C24—C25—C26	122.95 (18)
C21—C26—H26	120.3	C24—C25—N8	117.98 (18)
C1—C2—C3	119.56 (17)	C26—C25—N8	119.07 (18)
C1—C2—H2	120.2	C17—C18—C19	122.84 (18)
C3—C2—H2	120.2	C17—C18—N6	117.80 (18)
C22—C21—C26	119.44 (17)	C19—C18—N6	119.35 (19)

C4—C3—C2—C1	178.24 (13)	C10—C9—C8—C7	179.75 (18)
C2—C3—C4—C5	39.28 (13)	C8—C9—C10—C11ⁱⁱⁱ	39.15 (17)
C2ⁱ—C3—C4—C5	−140.72 (13)	C8—C9—C10—C11	−140.85 (17)

Symmetry codes: (i) −x+1/2, y, −z+1/2; (ii) x, y+1, z; (iii) −x+3/2, y, −z+1/2; (iv) x, y−1, z.

Experimental details

Crystal data
Chemical formula	[Mn₂(C₇H₃N₂O₆)₄(C₁₀H₈N₂)₂]
M_r	633.35
Crystal system, space group	Monoclinic, P2/n
Temperature (K)	293
a, b, c (Å)	10.0873 (6), 11.6336 (6), 21.2191 (12)
β (°)	98.075 (3)
V (Å³)	2465.41 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.62
Crystal size (mm)	0.82 × 0.45 × 0.35

Data collection
Diffractometer	Rigaku Mercury diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2000)
T_min, T_max	0.779, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	14626, 4334, 4149
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.085, 1.01
No. of reflections	4334
No. of parameters	393
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.37

Computer programs: CrystalClear (Rigaku, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

The authors would like to thank Fujian Provincial Science and Technology Innovation Foundation under Grant No 2007F3038 for financial support.

References

Mehrotra, R. C. & Bohra, R. (1983). Metal Carboxylates. London: Academic Press. Google Scholar
Rigaku (2000). CrystalClear and CrystalStructure. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shi, Z., Zhang, L. R., Gao, S., Yang, G., Hua, J., Gao, L. & Feng, S. (2000). Inorg. Chem. 39, 1990–1993. Web of Science CSD CrossRef PubMed CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.